US4243553A - Production of improved molybdenum disulfide catalysts - Google Patents
Production of improved molybdenum disulfide catalysts Download PDFInfo
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- US4243553A US4243553A US06/047,238 US4723879A US4243553A US 4243553 A US4243553 A US 4243553A US 4723879 A US4723879 A US 4723879A US 4243553 A US4243553 A US 4243553A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
- C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
- C07C1/0425—Catalysts; their physical properties
- C07C1/0445—Preparation; Activation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/02—Sulfur, selenium or tellurium; Compounds thereof
- C07C2527/04—Sulfides
- C07C2527/047—Sulfides with chromium, molybdenum, tungsten or polonium
- C07C2527/051—Molybdenum
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the invention relates to molybdenum disulfide catalysts. More particularly, it relates to the preparation of such catalysts having enhanced catalytic properties.
- a synthesis gas as from the gasification of coal with oxygen and steam.
- the gas stream Prior to methanation, the gas stream is commonly treated to provide a desired H 2 /CO ratio and to remove excess CO 2 and deleterious impurities such as sulfur impurities.
- the H 2 /CO ratio of the raw synthesis gas is generally substantially below the necessary minimum ratio of 3/1, at least a portion of the carbon monoxide is generally first reacted with steam, over an iron or other suitable catalyst in the well-known "water gas shift" reaction as follows:
- Excessive CO 2 in the gas stream is removed by conventional means, such as by treatment with alkaline absorbents.
- Sulfur impurities are also removed to substantially under 5 ppm, e.g. to less than about 1 ppm, preferably to less than 0.2 ppm, to protect the methanation catalyst from poisoning by such sulfur impurities.
- Hydrogen sulfide or other sulfur bearing gases are absorbed, selectively or non-selectively, by the absorben employed for carbon dioxide removal. When necessary, final cleanup may be accomplished by passing the gas stream through iron oxide, zinc oxide or activated carbon to remove residual traces of H 2 S or organic sulfides.
- the methanation catalysts currently being seriously considered for commercialization are based on nickel or cobalt as the active ingredient. These metallic catalysts are very active, selective and relatively cheap. They are, however, extremely sensitive to poisoning by sulfur compounds. Since almost all of the carbonaceous feeds employed for synthesis gas production contain sulfur that is converted largely to H 2 S during the initial gasification step, costly acid gas purification operations must be included in SNG process designs so as to lower the H 2 S level to the fractional ppm level indicated above to achieve commercially feasible, long catalyst life. It would be highly desirable in the art, therefore, if sulfur-resistant methanation catalysts were commercially available as this would permit a considerable reduction in the degree of gas purification processing required prior to the methanation step in SNG production operations. If such a catalyst would also catalyze water shift reaction (2) effectively, the number of individual processing steps, and the overall cost of SNG production could be even further reduced.
- molybdenum sulfide, MoS 2 , and tungsten sulfide, WS 2 , as well as more complex mixed sulfides, are sulfur-tolerant methanation catalysts.
- MoS 2 occurs native as molybdenite and can be prepared artifically by heating molybdenum dioxide, molybdenum trioxide or ammonium molybdate in H 2 S or sulfur vapor.
- Mills and Steffgen in Catalyst Rev. 8, 159 (1973), review the results of several studies with molybdenum and tungsten sulfide methanation catalysts prepared in a variety of ways. Even the best of these catalysts were only moderately active.
- Shultz et al also prepared catalysts by impregnating silica-alumina or activated carbon supports with ammonium molybdate, followed by calcining, to give a supported molybdenum oxide for which a conversion of 76.6% was reported at 420° C. and 21 atm. This catalyst was not sulfided. Other catalysts prepared as oxides by coprecipitating aluminum and molybdate salts, without sulfiding, provided methanation performance similar to that of impregnated materials.
- MoS 2 catalyst materials are relatively inactive, and are not generally considered to possess sufficient activity to justify use in commercial operations.
- sulfur resistant properties of MoS 2 materials therefore, such available materials have not been suitable for practical use in providing synthetic natural gas to meet existing and anticipated requirements for low-cost, high BTU gaseous heating fuels.
- High surface area molybdenum disulfide is produced by thermally decomposing a substituted ammonium thiomolybdate salt having the formula B 2 [MoO x S 4-x ], where B is a substituted aliphatic ammonium ion or a cyclic amine containing one or more basic N atoms, and x is 0, 1 or 2.
- Decomposition is carried out at temperatures of about 300°-800° C., preferably at about 400°-500° C., with the thiomolybdate salt being heated to the decomposition temperature so that a very slow heating rate, in an essentially oxygen-free atmosphere, is employed in the fairly narrow temperature interval in which the substantial portion of the particular substituted thiomolybdate salt decomposes.
- the MoS 2 of the invention can advantageously be employed as a water gas shift and/or methanation catalyst, and for us, particularly in nickel or cobalt promoted form, for catalyzing hydrogenation or hydrotreating reactions.
- the objects of the invention are accomplished by a novel process for the preparation of molybdenum disulfide, MoS 2 , having desirable properties for use as a methanation catalyst in addition to the sulfur resistant characteristics commonly associated with molybdenum disulfide.
- MoS 2 molybdenum disulfide
- Previously available MoS 2 does not have sufficient activity to warrant its consideration, on an overall technical and economic basis, as a methanation catalyst, in commercially feasible SNG operations.
- the present invention relates to the thermal decomposition of a selected substituted ammonium thiomolybdate salt under specific decomposition conditions to produce a MoS 2 catalyst material having desirable properties for water gas shift, methanation and other catalyst applications.
- the thiomolybdate salt has the formula B 2 [MoO x S 4-x ], where B is a substituted aliphatic ammonium ion containing from one to four alkyl groups or a cyclic amine containing one or more basic N atoms, and x is 0, 1 or 2.
- Illustrative examples of said substitutes aliphatic ammonium ions are those containing one alkyl group, such as where B + is n-C 4 H 9 NH 3 + , two alkyl groups, e.g., where B+ is (C 2 H 5 ) 2 NH 2 + , three alkyl groups, e.g., where B + is (CH 3 ) 3 NH + and four alkyl groups, e.g., where B + is (CH 3 ) 4 N + .
- thiomolybdate salts of this type utilized in the practice of the invention are (n-Butylamine) 2 H 2 MoS 4 , (Diethylamine) 2 H 2 MoS 4 , and tetramethyl ammonium thiomolybdate, [(CH 3 ) 4 N] 2 MoS 4 .
- suitable thiomolybdate salts in which B is the cation of a cyclic amine are those in which B contains one basic N atom, e.g., the piperidinium cation derived from piperidine and the pyrrolidinium cation derived from pyrrolidine, and in which B contains more than one basic N atom, e.g., the piperazinium cation derived from piperazine and the hexamethylenetetramonium cation derived from hexamethylenetetramine.
- substituted ammonium thiomolybdate salts suitable as the starting materials for use in the practice of the invention are known materials that can be prepared by synthesis techniques reported in the art. Such synthesis techniques do not form an essential part of the invention, which is directed to the production of improved MoS 2 catalyst materials by the decomposition of such known substituted ammonium thiomolybdate salts under the carefully controlled conditions herein disclosed and claimed. It will also be appreciated that other substituted ammonium thiomolybdate salts of the type herein described, apart from those referred to herein, may exist and also constitute suitable starting materials for use in the practice of the invention.
- the invention herein disclosed and claimed is directed to a process for producing a novel MoS 2 catalyst product having commercial application by the thermal decomposition of selected substituted ammonium thiomolybdate salts under controlled conditions.
- a form of bulk, high surface area molybdenum disulfide is formed that has superior catalytic properties for the water gas shift and methanation reactions compared with previously described MoS 2 catalysts prepared by previously known methods.
- the substituted ammonium thiomolybdate salts are decomposed, in the practice of the invention, at a decomposition temperature of from about 300° C. to about 800° C., preferably at a temperature of from about 400° C. to about 500° C. Contrary to the standard heating rate of 6°-10° C./min.
- molybdenum disulfide, MoS 2 having improved catalytic properties, is obtained when decomposition of the indicated substituted thiomolybdate salts, conveniently in the form of small pressed pellets rather than loose powder, is carried out by heating the salt very slowly through the temperature interval in which a major or substantial portion of the substituted thiomolybdate salt decomposes.
- This temperature interval in which very slow heating is required comprises a fairly narrow temperature range that will vary depending on the particular substituted thiomolybdate salt being decomposed in any given application of the invention.
- the temperature interval for any particular salt can readily be determined by heating the salt to the decomposition range indicated above and observing the fairly narrow temperature range during the course of such heating over which the major portion of the decomposition of the salt occurs.
- very slow heating is employed through the temperature range of from about 100° C. to about 200° C. in which a substantial portion of the salt decomposes.
- particular care must be taken to assure that decomposition through the indicated temperature interval of substantial decomposition is carried out in an essentially oxygen-free atmosphere.
- Such decomposition has been found to be advantageously carried out under vacuum in specific applications of the invention although other conventional means for maintaining an essentially oxygen-free atmosphere may be preferable in commercial operations.
- a nitrogen or argon atmosphere and to have hydrogen present within the range of from about 0 to 100% by volume based on the total volume of essentially oxygen-free atmosphere in the decomposition kiln or zone employed, conveniently with such hydrogen present in amounts up to about 10% by volume.
- a nitrogen or argon or hydrogen atmosphere e.g., conveniently with such hydrogen present in amounts up to about 10% by volume.
- the use of a nitrogen or argon or hydrogen atmosphere e.g., conveniently supplied by forming gas, must be carefully controlled to assure that the atmosphere is essentially oxygen-free as is achieved in other embodiments by carrying out the decomposition under vacuum.
- decomposition of the indicated substituted thiomolybdate salts is advantageously carried out by heating the salts at a rate of from about 0.5° to about 2° C./min. through the temperature interval in which a major or substantial portion of the substituted thiomolybdate salt decomposes. It will be appreciated by those skilled in the art that, in commercial applications of the invention, operations outside this narrow range may be permissible because of the particular characteristics and performance capability of the particular kiln or other decomposition apparatus employed in practical commercial-scale operations.
- Very slow heating of the particular substituted thiomolybdate salt through the temperature range of substantial decomposition should be observed in any event, whether within the observed range of from about 0.5° to about 2° C./min. or such other slow heating rate as may pertain to any given commercial application of the invention.
- Higher heating rates can be employed at temperatures both below and above the narrow temperature interval at which decomposition of the salt essentially occurs.
- the product molybdenum disulfide is obtained as a high surface area product having desirable catalytic properties.
- the MoS 2 product will thus have a surface area of from about 25 to about 150 m 2 /gm. It should be noted, however, that the high surface area is a factor, but only one factor, in the improved catalytic properties resulting from the production of MoS 2 in accordance with the present invention. The improved properties result, to the contrary, from the particular decomposition conditions employed with the particular substituted ammonium thiomolybdate salts disclosed herein.
- Such conditions result in the production of an active MoS 2 catalytic product that is obtained in bulk, high surface area form.
- the decomposition conditions of the invention do not result in improved catalytic properties of MoS 2 product from all thiomolybdate salts, however, but expectedly achieve such results with those herein disclosed as falling within the scope of the invention.
- Hexamethylenetetramine thiomolybdate was prepared by the procedures of Udupa, et al., Curr. Sci. 42, 676 (1973) and of Dembicka, et al., Rocz. Chem. 49, 1475 (1975). Both syntheses involved the treatment of hexamethylene-tetramine molybdate solutions with hydrogen sulfide. Using hydrazine as the salt, hydrazinium thiomolybdate, (N 2 H 4 ) 2 H 2 MoS 4 , was prepared by the method of Udupa, et al.
- the tetramethyl-ammonium hydroxide salt proved difficult to prepare reproducibly as a result of mixed phases, poorly crystalline products, and/or low yields.
- An acceptable, but not optimum, procedure consisted of treating a solution consisting of 150 g of tetramethylammonium hydroxide pentahydrate, 20 g of molybdenum trioxide and 500 ml of water with H 2 S at less than 10° C.
- the thiomolybdate salts of the invention were converted to MoS 2 products, or doped variations thereof, by heating said salts to a decomposition temperature of 400°-500° C., with the salts being heated at a rate within the range of from about 0.5° to 2° C., in an essentially oxygen-free atmosphere, i.e., under vacuum, through the relatively narrow temperature range or interval at which the salt essentially decomposes and a majority of its weight is lost. Further heating to the indicated decomposition temperature assured that the decomposition was complete, and the retention of residual sulfur was avoided.
- the salts were held at decomposition temperature for 1-3 hours, then cooled to room temperature either under nitrogen or H 2 /argon.
- the MoS 2 thus produced was pelletized for catalytic evaluation by either pressing into 1/8" diameter ⁇ 1/8" long cylinders, or by forming 1/2" diameter ⁇ 3/4" cylinders that were subsequently crushed and sized to 10/20 mesh.
- Catalysts prepared in accordance with the invention have been evaluated in a tubular reactor under varying conditions of temperature, pressure, CO:H 2 ratio and gas hourly space velocity (SV in hr. -1 ). Conditions of 400° C. outlet temperature, 400 psig. CO:H 2 ratios of 1:3 and SV of 3300 hr. -1 were most commonly employed. The advantages of the invention were demonstrated by comparing performance data obtained by means of MoS 2 prepared in accordance with the invention with MoS 2 prepared by methods believed representative of the prior art teachings as indicated above. The reactor employed was a one cm. I.D.
- reactor containing approximately 15 ml., typically about 20 grams, of catalyst, a back-pressure regulator that maintained the system at a preset constant pressure, a differential flow controller-needle valve combination that maintained a constant flow into the system, and an on-line gas chromatograph and wet test meter to monitor the composition and volume of the product stream.
- the reactor was mounted vertically in an 8" Lindberg clamshell furnace having a 1" bore.
- the temperature of the reactor was maintained with a West SCR Stepless Controller via a thermocouple attached to the outside of the reactor.
- Catalyst temperature was measured by a second thermocouple mounted axially in the reactor with the tip about one cm. from the bottom of the bed.
- the sulfide catalysts were significantly more active for the water gas shift reaction, i.e., reaction (2), than for methanation, i.e., reaction (1). Reflecting this, two measures of catalyst performance were used for evaluation purposes. These were (a) the percent of the CO fed to the system that was converted to hydrocarbons, e.g., methane, ethane, propane, and (b) total CO conversion, i.e., the amount of CO converted to hydrocarbons plus the amount consumed by the shift reaction. Surface areas were determined by a single point BET method using a Quantachrom Monosorb Analyzer. The catalytic performance of the various MoS 2 types is summarized in the table below:
- the state-of-the-art catalysts i.e., catalysts 1-4
- the MoS 2 catalysts of the invention i.e., catalysts 5-13
- the activities and stabilities of the amine-derived samples were remarkably similar considering the wide range of structure types, composition and basicity represented in the parent amines.
- modifications can be employed to enhance the stability of the catalyst.
- Such modifications include decomposing the substituted ammonium thiomolybdate salt in admixture with an inert, preformed particulate diluent, bulk doping the thiomolybdate salt, as with tungsten or vanadium, prior to decomposition, or mixing the MoS 2 catalyst product with a suitable catalyst support additive, and suitable binders as required, for desired support and/or dispersion of the active catalyst material.
- catalyst life may be extended by retarding the effects of sintering that lead to a decrease in the amount of exposed catalyst surface, which, in turn, leads to a decrease in catalytic activity.
- a preformed colloidal ZrO 2 can be added to the selected substituted ammonium thiomolybdate salt preparation, followed by the indicated thermal decomposition of the invention, to produce a matrixed MoS 2 , i.e., a MoS 2 -ZrO 2 material, having comparable activity and some improvement in long-term stability as compared with MoS 2 product not so matrixed.
- a cubic yttria-stabilized zirconia prepared by the process disclosed in U.S. Pat. No. 4,065,544, can be employed in slurry form for this purpose.
- Silica can also be employed as another example of a suitable inert, preformed particulate diluent.
- MoS 2 prepared in accordance with the invention can also be bulk doped with tungsten or vanadium to achieve desirable stability characteristics in the MoS 2 catalyst product.
- the tungsten doped MoS 2 obtained by decomposing a doped, Mo-containing salt of the above formula is Mo y W 1-y S 2 , where y is generally from about 0.5 to about 0.9.
- replacement of some of the substituted ammonium thiomolybdate salt by V 2 O 5 leads to mixed Mo-V thiosalts from which vanadium doped products having the formula Mo y V 1-y S 2 , where y is likewise generally from about 0.5 to about 0.9.
- the decomposition products of the invention have the approximate composition MoS 2 , but departures from ideal stoichiometry may occur as a result of (a) incomplete removal of sulfur during catalyst preparation, resulting in S:Mo ratios of greater than two, (b) oxidation of the catalyst surfaces when exposed to moist air, or (c) slow changes that may occur during catalytic use, such as the formation of Mo and H 2 S by reaction of MoS 2 with hydrogen, or the formation of MoO 2 and H 2 S by the reaction of MoS 2 with water.
- the feed gas for water gas shift and methanation activities using the sulfur-resistant MoS 2 catalyst of the invention can be that generated in a variety of commercial operations, such as (1) various coal gasification processes known in the art, (2) waste disposal systems, e.g., the Union Carbide Corporation PUROXTM System for high temperature incineration and pyrolysis of refuse, and (3) metallurgical operations such as blast furnaces, phosphorous furnaces, metal carbide furnaces and the like.
- the effluent gases from such operations will normally contain CO and H 2 , generally within the molecular ratio range of 1:1-1:3, diluents, such as CO 2 , N 2 and H 2 O, and potential poisons such as H 2 S.
- the MoS 2 catalysts of the invention operate successfully across a wide range of feed compositions.
- the tolerable H 2 S level can vary from a few ppm to several percent, with the active MoS 2 catalyst of the invention having the advantage that the higher levels of H 2 S content in the feed gas do not effectively destroy its activity as occurs in the use of other, less sulfur-resistant, methanation catalyst materials.
- water is a mild inhibitor, preferred feeds to the catalyst will avoid unnecessary steam addition over that needed from stoichiometric considerations.
- the actual feed composition to the catalyst will be determined by various pertinent factors such as the optimum balance between available feed compositions, extent of steam addition required and recycle ratios.
- the MoS 2 catalyst can be employed in any suitable form, as for example in pelleted form in a fixed-bed reactor, with conversion to more attrition-resistant form as hereinabove indicated and with appropriate use of inert, conventional binders as desired, or in finely divided form in a fluidized bed or liquid slurry reactor.
- molybdenum sulfide catalysts prepared under the controlled thermal decomposition conditions of the invention have also been found desirable for use in catalyzed hydrogenation and hydrotreating reactions.
- molybdenum oxides have commonly been converted to the sulfide form prior to or during use, with the molybdenum sulfide being supported on a ⁇ -alumina carrier.
- Cobalt and/or nickel sulfide is also present as a promoter.
- Cobalt and/or nickel-promoted MoS 2 catalysts prepared by the thiosalt precursor method of the invention have been found to have significantly higher activity than existing commercial products.
- the hydrodenitrogenation activity of the MoS 2 catalysts of the invention for petroleum feedstock can be demonstrated by preparing such catalysts, in conventional nickel promoted form, using the selected substituted thiomolybdate salt, nickel acetate, Ni(Ac) 2 .4H 2 O, NH 4 OH and water.
- the nickel acetate, ammonium hydroxide and water can be combined, and the selected salt added thereto.
- the mixture can then be cooled, as in an ice bath, and H 2 S can then be bubbled therein until consumption of H 2 S, and precipitation of NiS, ceases.
- the precipitate can be filtered, washed with denatured alcohol and dried, e.g., at 80° C. overnight.
- the combined powders thus obtained can be blended in a mill, mixed by rolling, pelletized and then reduced with very slow heating, e.g., at a rate of between about 0.5° and about 2° C., in a carefully controlled non-oxygen atmosphere, as by vacuum or other suitable means, in the temperature interval in which a substantial portion of the substituted thiomolybdate salt decomposes.
- the desirable hydrotreating, i.e. hydrodesulfurization and/or hydrodenitrogenation, and hydrogenation activities of the MoS 2 product of the invention, particularly when employed in nickel or cobalt-promoted form, will readily be appreciated in practical commercial operations. It will be understood that the promoted catalysts can be prepared from the selected substituted ammonium thiomolybdate salts by various impregnation and precipitation procedures falling within the scope of the invention as herein disclosed and claimed.
- nickel or cobalt-promoted catalyst it is convenient to form the nickel or cobalt-promoted catalyst by precipitating NiS or CoS in the presence of a selected ammonium thiomolybdate salt, and thereafter thermally treating the mixture to convert the substituted ammonium thiomolybdate salt to the highly desirable form of MoS 2 produced in the recited process.
- the nickel or cobalt-promoted catalysts can be prepared with various amounts of nickel or cobalt present for the intended purpose as is known in the art. It should be noted that nickel or cobalt acetates have been added to reaction mixtures in amounts corresponding to a promoter/molybdenum mole ratio of 0.4 for maximum hydrodesulfurization activity in operations utilizing prior art MoS 2 catalyst compositions.
- the hydrogenation activity of the MoS 2 catalysts of the invention is demonstrated thereby and can be further demonstrated by the use of such catalysts, in promoted and unpromoted form, in the hydrogenation of representative feedstocks, such as methyl-naphthalene.
- the improved hydrodesulfurization and hydrodenitrogenation of liquid fuels will be needed when it becomes necessary to process lower grade petroleum feedstocks and the alternate fuel sources, such as liquefied coal, shale oil, tar sands, and the like, that are under consideration as replacements for petroleum.
- the MoS 2 catalysts prepared in accordance with the invention are of significance, therefore, in a number of highly important applications related to the ever-growing search of new and improved technologies for meeting the energy and chemical feedstock requirements of industrial societies.
Abstract
Description
CO+3H.sub.2 →CH.sub.4 +H.sub.2 O, (1)
CO+H.sub.2 O→CO.sub.2 +H.sub.2. (2)
CO.sub.2 +4H.sub.2 →CH.sub.4 +2H.sub.2 O and/or (3)
2CO+2H.sub.2 →CH.sub.4 +CO.sub.2. (4)
TABLE ______________________________________ Catalytic Performance After Initial Overnight Performance.sup.(a) Operation % % CO to CO to Hydro- Hydro- car- % CO car- % CO Catalyst Type bons Conv. bons Conv. ______________________________________ 1. Commercial MoS.sub.2 nil nil -- -- 2. Sulfided Ammonium Paramolybdate (APM) 36 63 -- -- 3. Sulfided MoO.sub.3 /Al.sub.2 O.sub.3 48 82 -- -- 4. Sulfided Climax 30 54 -- -- Mo--MoO.sub.2 5. (Piperazine).sub.2 H.sub.2 MoS.sub.4 69 94 68 93 6. (Piperazine)H.sub.2 MoS.sub.4 58 87 59 88 7. (Piperazine)H.sub.2 MoOS.sub.3 66 93 60 88 8. (Piperazine).sub.2 H.sub.2 MoS.sub.4 58 87 59 88 9. (Pyrrolidine).sub.2 H.sub.2 MoOS.sub.3 61 90 57 87 10. (n-Butylamine).sub.2 H.sub.2 MoS.sub.4 66 93 56 85 11. (Diethylamine).sub.2 H.sub.2 MoS.sub.4 67 93 60 86 12. Autoclaved Piperazine Product 71 95 59 86 13. Tetramethylammonium Thiomolybdate 67 96 67 96 ______________________________________ .sup.(a) 400° C. outlet; 400 psig; CO:H.sub.2-1 = 1:3; Space Velocity; SV 3000 hr. except that catalyst type 5 was tested at 500° C.
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Cited By (86)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4303634A (en) * | 1979-09-07 | 1981-12-01 | Uop Inc. | Method of catalyst preparation |
US4430442A (en) | 1982-07-20 | 1984-02-07 | Exxon Research And Engineering Co. | Catalysts from molybdenum polysulfide precursors and their preparation |
US4430443A (en) | 1982-07-20 | 1984-02-07 | Exxon Research And Engineering Co. | Supported carbon-containing molybdenum and tungsten sulfide catalysts, their preparation and use |
US4431747A (en) * | 1982-07-20 | 1984-02-14 | Exxon Research And Engineering Co. | Supported carbon-containing molybdenum and tungsten sulfide catalysts, their preparation and use |
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